<?xml version="1.0" encoding="UTF-8"?><!DOCTYPE article  PUBLIC "-//NLM//DTD Journal Publishing DTD v3.0 20080202//EN" "http://dtd.nlm.nih.gov/publishing/3.0/journalpublishing3.dtd"><article xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink" dtd-version="3.0" xml:lang="en" article-type="research article"><front><journal-meta><journal-id journal-id-type="publisher-id">OPJ</journal-id><journal-title-group><journal-title>Optics and Photonics Journal</journal-title></journal-title-group><issn pub-type="epub">2160-8881</issn><publisher><publisher-name>Scientific Research Publishing</publisher-name></publisher></journal-meta><article-meta><article-id pub-id-type="doi">10.4236/opj.2016.68B011</article-id><article-id pub-id-type="publisher-id">OPJ-70303</article-id><article-categories><subj-group subj-group-type="heading"><subject>Articles</subject></subj-group><subj-group subj-group-type="Discipline-v2"><subject>Chemistry&amp;Materials Science</subject><subject> Engineering</subject><subject> Physics&amp;Mathematics</subject></subj-group></article-categories><title-group><article-title>
 
 
  Fabrication and Investigation of the Magnetic Properties of Co and Co3O4 Nanoparticles
 
</article-title></title-group><contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Fardin</surname><given-names>Taghizadeh</given-names></name><xref ref-type="aff" rid="aff1"><sub>1</sub></xref></contrib></contrib-group><aff id="aff1"><label>1</label><addr-line>Department of Physics, College of Sciences, Yasouj University, Yasouj, Iran</addr-line></aff><author-notes><corresp id="cor1">* E-mail:</corresp></author-notes><pub-date pub-type="epub"><day>25</day><month>08</month><year>2016</year></pub-date><volume>06</volume><issue>08</issue><fpage>62</fpage><lpage>68</lpage><history><date date-type="received"><day>19</day>	<month>May</month>	<year>2016</year></date><date date-type="rev-recd"><day>accepted</day>	<month>18</month>	<year>August</year>	</date><date date-type="accepted"><day>25</day>	<month>August</month>	<year>2016</year></date></history><permissions><copyright-statement>&#169; Copyright  2014 by authors and Scientific Research Publishing Inc. </copyright-statement><copyright-year>2014</copyright-year><license><license-p>This work is licensed under the Creative Commons Attribution International License (CC BY). http://creativecommons.org/licenses/by/4.0/</license-p></license></permissions><abstract><p>
 
 
   
   The nanoparticles exhibit some novel optical and magnetic properties, which are different from its bulk material. Cobalt oxide has been known as a semi-conductor compound of p type with a Spinel structure. Therefore, they are used as gas sensor an
   d absorbent of solar energy. Furthermore, they are employed as an effective catalyzer in environmental clearing. In the thermal gradation method, carbonyl cobalt Co2(CO)8 is often used as a precursor, though cobalt carbonyl is very toxic and expensive. Magnetic compounds have been among interesting issues for human beings for over 4000 years. In large societies, magnetic compounds including computer disks, credit cards, speakers, coolers, automatic doors, and many other devices can be observed on a daily basis. The structure and morphology of as-prepared Co3O4 nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). The TEM images showed that the product nanoparticles consisted of dispersive quasi- spherical particles with a narrow size distribution ranged from 5 to 15 nm and an average size around 10 nm. The magnetic measurements confirmed that the Co3O4 nanoparticles show a little ferromagnetic behavior which could be attributed to the uncompensated surface spins and finite size effects. The ferromagnetic order of the Co3O4 nanoparticles is raised with increasing the decomposition temperature. 
  
 
</p></abstract><kwd-group><kwd>Magnetic Properties</kwd><kwd> Nano Particles</kwd><kwd> Fabrication Method</kwd><kwd> Co3O4</kwd></kwd-group></article-meta></front><body><sec id="s1"><title>1. Introduction</title><p>In recent years, metal cobalt (Co) and cobalt oxide (Co<sub>3</sub>O<sub>4</sub>) have attracted a great deal of attention thanks to their special properties. Based on these special properties, they have a wide range of applications including sensors, the components of information storage, catalyzers, etc. [<xref ref-type="bibr" rid="scirp.70303-ref1">1</xref>] [<xref ref-type="bibr" rid="scirp.70303-ref2">2</xref>]. Cobalt oxide has been known as a semi-conduc- tor compound of p type with a Spinel structure. Therefore, they are used as gas sensor and absorbent of solar energy. Furthermore, they are employed as an effective catalyze in environmental clearing [<xref ref-type="bibr" rid="scirp.70303-ref3">3</xref>]-[<xref ref-type="bibr" rid="scirp.70303-ref6">6</xref>]. Metal cobalt is important owing to its various crystal structures (fcc, hcp, ε), the type of the structure of cobalt affects its magnetic and electronic properties [<xref ref-type="bibr" rid="scirp.70303-ref7">7</xref>]. The important point in fabrication of pure metals is their stability against oxidation. This is because as the size of particles declines, their resistance to oxidation diminishes as well. Recently, walked into particles have been prepared by some methods including thermal degradation [<xref ref-type="bibr" rid="scirp.70303-ref7">7</xref>] [<xref ref-type="bibr" rid="scirp.70303-ref8">8</xref>], vapor condensation [<xref ref-type="bibr" rid="scirp.70303-ref9">9</xref>] [<xref ref-type="bibr" rid="scirp.70303-ref10">10</xref>], decreased salt of cobalt [<xref ref-type="bibr" rid="scirp.70303-ref11">11</xref>] [<xref ref-type="bibr" rid="scirp.70303-ref12">12</xref>], and deposition method [<xref ref-type="bibr" rid="scirp.70303-ref13">13</xref>].</p><p>In the thermal gradation method, carbonyl cobalt Co<sub>2</sub>(CO)<sub>8</sub> is often used as a precursor, though cobalt carbonyl is very toxic and expensive. Recently, Shao et al conducted thermal degradation using cobalt acetate with cobalt nanoparticles of 8 - 200 nm [<xref ref-type="bibr" rid="scirp.70303-ref14">14</xref>]. Similarly, Lee et al have prepared cobalt nanoparticles through thermolysis of Co<sup>2+</sup>-Oleat<sub>2</sub> [<xref ref-type="bibr" rid="scirp.70303-ref15">15</xref>]. In order to prevent clotting of the particles, organic surfactants are used [<xref ref-type="bibr" rid="scirp.70303-ref7">7</xref>]. Triphenyl phosphine (TPP) is widely used for stabilizing gold nanoparticles and other metals [<xref ref-type="bibr" rid="scirp.70303-ref16">16</xref>]. The phenyl groups in TPP develop more spatial disturbance than chain alkyl groups [<xref ref-type="bibr" rid="scirp.70303-ref17">17</xref>].</p></sec><sec id="s2"><title>2. Method of Fabrication</title><p>In materials science, the sol-gel process is a method for producing solid materials from small molecules (<xref ref-type="fig" rid="fig1">Figure 1</xref>). The method is used for the fabrication of metal oxides, especially the oxide of cobalt.</p><p>The process involves conversion of monomers into a colloidal solution (sol) that acts as the precursor for an integrated network (or gel) of either discrete particles or network polymers.In this method, metal nanoparticles and the metal oxide have been prepared through thermal degradation of the metal-surfactant complex in a hot surfactant solution. This method is schematically shown in <xref ref-type="fig" rid="fig2">Figure 2</xref>, demonstrating the fabrication of cobalt nanoparticles.</p><fig-group id="fig1"><label><xref ref-type="fig" rid="fig1">Figure 1</xref></label><caption><title>The sol-gel method for fabrication of nanoparticles</title></caption><fig id ="fig1_1"><label></label><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/70303x14.png"/></fig></fig-group><fig-group id="fig2"><label><xref ref-type="fig" rid="fig2">Figure 2</xref></label><caption><title>The procedure of fabrication of Co<sub>3</sub>O<sub>4</sub> nanoparticles</title></caption><fig id ="fig2_1"><label></label><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/70303x4.png"/></fig></fig-group></sec><sec id="s3"><title>3. Magnetic Properties</title><p>Firstly, the magnetic properties and hysteresis loops of magnetic compounds are generally discussed, followed by investigation of the properties of cobalt and cobalt oxide nanoparticles.</p><p>Magnetic compounds have been among interesting issues for human beings for over 4000 years. In large societies, magnetic compounds including computer disks, credit cards, speakers, coolers, automatic doors, and many other devices can be observed on a daily basis [<xref ref-type="bibr" rid="scirp.70303-ref18">18</xref>].</p><p>There are various magnetic compounds including diamagnetic, paramagnetic, and ferromagnetic. Further, ferromagnetic itself is categorized into two smaller groups called anti-ferromagnetic and ferrimagnetic. When magnetic moments are positioned randomly in relation to each other, the pure magnetic moments of the Crystal is zero. This state is called paramagnetic. However, the ferromagnetic crystal has a pure magnetic moment. The ferrimagnetic crystal also has a pure magnetic moments, but magnetic areas are positioned at opposite directions to each other. One of the areas is larger than the other and thus eventually a net magnetic moment will be present. However, in the antiferromagnetic crystal, the magnetic areas are absolutely of the same size and in opposite direction. Two important properties of magnetic compounds are Curie temperature and magnetic hysteresis. Exchanged coupling and thus the Heisenberg’s exchange energy are directly related to Curie temperature (T<sub>c</sub>) of ferro and ferrimagnetic compounds. At temperatures lower than T<sub>c</sub>, the magnetic moment is the same as the specific crystallographic direction of the zero axis of these compounds. It is preferred that this axis be called easy axis of magnetic crystal. This axis is developed in response to pairing this electron spin and the angular momentum of electron orbital. Due to presence of the easy axis, by applying an external magnetic field, the formation of the crystal of the compounds is controlled. When the magnetic field with the crystal’s easy axis and its direction towards the external magnetic field overcome the barrier energy between the magnetic areas, it changes their direction towards the magnetic field. This barrier energy is known as Magnetocrystalline Anisotropy, the atomic region of the magnetic hysteresis behavior of magnetic compounds. E<sub>A</sub> is one of the most important principles of the magnetic properties of compounds, determining the stability of compounds for special uses [<xref ref-type="bibr" rid="scirp.70303-ref18">18</xref>].</p><p>Ferromagnetic compounds are of interest based on their applications. Their properties should be identified quantitatively using the hysteresis loop of magnetic compounds. A hysteresis loop can be measured by placing a sample in a magnetometer and the compound’s response (M, σ) to the exerted magnetic field (H). Several quantities can be obtained from the hysteresis loop [<xref ref-type="bibr" rid="scirp.70303-ref19">19</xref>].</p><p>Magnetic saturation (M<sub>s</sub>) or special magnetic saturation (σ<sub>s</sub>) are the cases that show the extent of magnetization when all bipolars have been ordered in the direction of the exerted magnetic field.</p><p>The remaining magnetic (M<sub>r</sub>) is the magnetization of the sample in a magnetic field of zero. The inhibition force (H<sub>c</sub>) is a force of the magnetic field required for changing the remaining magnetization. The change in the field's bias (H<sub>E</sub>) indicates the extent of displacement off the center of hysteresis loop.</p><p><xref ref-type="fig" rid="fig3">Figure 3</xref> demonstrates the magnetization curve of a ferromagnetic compound. The total changes of magnetization of the sample M has been shown in terms of the intensity of the exerted DC field (H). Initially, when the</p><fig id="fig3"  position="float"><label><xref ref-type="fig" rid="fig3">Figure 3</xref></label><caption><title> Hysteresis curve of a ferromagnetic</title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/70303x5.png"/></fig><p>exerted field increases, so does M, until it reaches the saturation point M<sub>s</sub>. When the exerted field decreases from the saturation point, M does not reach its initial value, rather it stops at a point higher than the reduced field. This condition is called “residual”. It happens when the areas that have been aligned with the increase in the field do not return to their original orientation with the reduction of the field. When the exerted magnetic field H reaches zero, the magnet has still magnetization called residual magnetization (M<sub>r</sub>). As can be seen in <xref ref-type="fig" rid="fig3">Figure 3</xref>, in order to remove the residual magnetization, the H<sub>c</sub> field should be exerted in the opposite direction of the initial field. This field is called driving field, which causes the areas to rotate and return to their original positions. The properties of the magnetization curve of a ferromagnetic compound is a strong reliance for applying magnetic compounds.</p><p>Originally, the magnetic properties of compounds can be understood and controlled through magnetic pairings. Such pairings have a close relationship with the type of the chemical compound and the magnetic structure of compounds, though no accurate relationship is known between the magnetic properties of compounds, their chemical composition, and their crystal structures at an atomic level. There are various factors contributing to proper understanding of the changes of magnetic areas at atomic level by external exerted fields as well as the magnetic properties and magnetic pairings at atomic level. The structure of magnetic nanoparticles includes unique magnetic areas. Multi-area structures are not desirable in terms of energy due to their small size. Without the presence of the walls of areas, the magnetic pairing of atomic balance is directly associated with the magnetic properties of nanoparticles. Certainly, understanding and controlling the magnetic properties of nanoparticles will clarify the mechanism of magnetic properties of compounds together with its design and control. Magnetic nanoparticles are promising thanks to reduction of magnetic areas and thus development of super-paramagnetic properties. The super-paramagnetic properties of nanoparticles are directly influenced by magnetic Anisotropy of nanoparticles. As is evident in <xref ref-type="fig" rid="fig3">Figure 3</xref>, due to the symmetry of the precursor, there are sites with equal energy balances on the surface of the metal kernel. TPP is a surfactant with a high boiling point, developing a great spatial inhibition of controlling the magnetic properties of magnetic nanoparticles, despite the three phenyl groups. In addition to TPP in the mixture, presence of oleyl amine and the complexity of the precursor significantly diminish the size of particles. Oleyl amine is known as a ligand that has a suitable bond with the surface of metal nanoparticles. The combination of the effects of TPP and oleyl amine greatly contributes to development of individual nanoparticles.</p></sec><sec id="s4"><title>4. Results and Discussion</title><sec id="s4_1"><title>4.1. Magnetic Results</title><p>As shown in <xref ref-type="fig" rid="fig4">Figure 4</xref> the curve exhibits an antiferromagnetic behavior. The ferromagnetic behavior of the nanoparticles can be explained as follows: bulk Co<sub>3</sub>O<sub>4</sub> has a normal spinel structure with antiferromagnetic exchange between ions which occupy the tetrahedral and octahedral sites [<xref ref-type="bibr" rid="scirp.70303-ref19">19</xref>].</p><fig id="fig4"  position="float"><label><xref ref-type="fig" rid="fig4">Figure 4</xref></label><caption><title> CompoundCo<sub>3</sub>O<sub>4</sub> nanoparticles [<xref ref-type="bibr" rid="scirp.70303-ref18">18</xref>]</title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/70303x6.png"/></fig><p>The hysteresis curve for Co<sub>3</sub>O<sub>4</sub> nanoparticles prepared at different temperatures were carried out at room temperature. As shown in <xref ref-type="fig" rid="fig5">Figure 5</xref> the hysteresis curve for the Co<sub>3</sub>O<sub>4</sub> nanoparticles prepared at 400 k exhibits a weak ferromagnetic behavior with a saturation magnetization of 0.125 emu∙g<sup>−1</sup> at the maximum field of 9 kOe applied while the hysteresis curve for the Co<sub>3</sub>O<sub>4</sub> samples prepared at 450 K and 500 K in the <xref ref-type="fig" rid="fig6">Figure 6</xref> and <xref ref-type="fig" rid="fig7">Figure 7</xref> display higher ferromagnetic properties with saturation magnetization values of 0.23 and 0.31 emu∙g<sup>−1</sup> at the applied field of 9 kOe, respectively. To confirm that the ferromagnetic behavior originates from the nanoparticles, this measurement was also conducted on a bulk sample.</p><p>The change from an antiferromagnetic state for bulk Co<sub>3</sub>O<sub>4</sub> to a weakly ferromagnetic state for the Co<sub>3</sub>O<sub>4</sub> nanoparticles can be ascribed to the uncompensated surface spins and finite size effects. It is well known.</p><fig id="fig5"  position="float"><label><xref ref-type="fig" rid="fig5">Figure 5</xref></label><caption><title> The hysteresis curve of Co<sub>3</sub>O<sub>4</sub> nanoparticles at 400 K</title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/70303x7.png"/></fig><fig id="fig6"  position="float"><label><xref ref-type="fig" rid="fig6">Figure 6</xref></label><caption><title> The hysteresis curve of Co<sub>3</sub>O<sub>4</sub> nanoparticles at 450 K</title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/70303x8.png"/></fig><fig id="fig7"  position="float"><label><xref ref-type="fig" rid="fig7">Figure 7</xref></label><caption><title> The hysteresis curve of Co<sub>3</sub>O<sub>4</sub> nanoparticles at 500 K</title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/70303x9.png"/></fig></sec><sec id="s4_2"><title>4.2. XRD Results</title><p><xref ref-type="fig" rid="fig8">Figure 8</xref> presents the X-ray Diffraction (XRD) pattern on the prepared samples. The peaks in <xref ref-type="fig" rid="fig8">Figure 8</xref> are related to 111, 200, 220, 200, and 311 planes of hcp cobalt. Due to the very small size, cobalt nanoparticles are easily oxidized when exposed to air. The XRD pattern reveals no peaks related to the cobalt oxide phase.</p><p>This is due to the protection of the surface of cobaltnanoparticles against oxidation by oleyl amine and TPP. The developed peaks are wide, attributable to the reduction in the size of particles. This shows that all cobalt particles are in nano size. It is possible to obtain the mean size of the particles by Debye-Scherrer Equation. The mean size of these samples is 20 nm. <xref ref-type="fig" rid="fig9">Figure 9</xref> demonstrates the XRD pattern of cobalt nanoparticles following exposure to air. In this figure, no peak associated with metal cobalt can be seen. The image is related to the cubic phase of Co<sub>3</sub>O<sub>4</sub> with a Spinel structure. The network parameter is equal to a = 8.085 &#197;. No other pure peak is seen in this pattern, suggesting that the Co<sub>3</sub>O<sub>4</sub> is completely pure. Separation of peaks is very good, implying that the crystal structure is single phased in the cubic crystal structure.</p></sec><sec id="s4_3"><title>4.3. TEM Results</title><p><xref ref-type="fig" rid="fig1">Figure 1</xref>0 illustrates the TEM image of cobalt nanoparticles. The majority of Co<sub>3</sub>O<sub>4</sub> nanoparticles are irregular (<xref ref-type="fig" rid="fig1">Figure 1</xref>0). The mean size of Co<sub>3</sub>O<sub>4</sub> nanoparticles is 10 nm.In HRTEM image (<xref ref-type="fig" rid="fig1">Figure 1</xref>1), the distance be-</p><fig id="fig8"  position="float"><label><xref ref-type="fig" rid="fig8">Figure 8</xref></label><caption><title> The XRD pattern of Co</title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/70303x10.png"/></fig><fig id="fig9"  position="float"><label><xref ref-type="fig" rid="fig9">Figure 9</xref></label><caption><title> The XRD pattern of Co<sub>3</sub>O<sub>4</sub> nanoparticles</title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/70303x11.png"/></fig><fig id="fig10"  position="float"><label><xref ref-type="fig" rid="fig1">Figure 1</xref>0</label><caption><title> TEM image of Co<sub>3</sub>O<sub>4</sub> nanoparticles</title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/70303x12.png"/></fig><fig id="fig11"  position="float"><label><xref ref-type="fig" rid="fig1">Figure 1</xref>1</label><caption><title> HRTEM image of Co<sub>3</sub>O<sub>4</sub> nanoparticles</title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/70303x13.png"/></fig><p>tween the two adjacent planes (d) is 4.6 A. The TEM images showed that the product nanoparticles consisted of dispersive quasi-spherical particles with a narrow size distribution ranged from 5 to 15 nm and an average size around 10 nm.</p></sec></sec><sec id="s5"><title>Cite this paper</title><p>Fardin Taghizadeh, (2016) Fabrication and Investigation of the Magnetic Properties of Co and Co3O4 Nanoparticles. Optics and Photonics Journal,06,62-68. doi: 10.4236/opj.2016.68B011</p></sec></body><back><ref-list><title>References</title><ref id="scirp.70303-ref1"><label>1</label><mixed-citation publication-type="other" xlink:type="simple">[1]	Casas-Cabanas, M., Binotto, G., Larcher, D., Lecup, A., Giordani, V. and Tarascon, J.M. (2009) Defect Chemistry and Catalytic Activity of Nanosized Co3O4. Chem Mater, 20, 1939-1947. http://dx.doi.org/10.1021/cm900328g</mixed-citation></ref><ref id="scirp.70303-ref2"><label>2</label><mixed-citation publication-type="other" xlink:type="simple">Askarinejad, A., Bagherzadeh, M. and Morsali, A. 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